9-甲酰基芴肟 | 24252-72-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 中文名称: 9-甲酰基芴肟
• 英文名称: 9-formylfluorene oxime
• 英文别名: 9-Formylfluoren-β-oxim；9-Formylfluoren-oxim；(NZ)-N-(9H-fluoren-9-ylmethylidene)hydroxylamine
• CAS: 24252-72-0
• 化学式: C₁₄H₁₁NO
• 分子量: 209.247
• InChiKey: HHXFPUAHUDLFEA-DHDCSXOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  9-甲酰基芴肟 在 羟胺 作用下， 以 水 为溶剂， 生成 fluorene-9-carbaldehyde
  参考文献：
  名称：

  Rate and equilibrium constants for formation and hydrolysis of 9-formylfluorene oxime: diffusion-controlled trapping of a protonated aldehyde by hydroxylamine

  摘要：

  Equilibrium constants K-add = 440 and K-ox = 3.0 X 10(8) for formation of a carbinolamine adduct and oxime, respectively from 9-formylfluorene and hydroxylamine, and pK(a) = -1.62 for protonation of the oxime, have been evaluated at 25 degreesC in aqueous solution, based on measurements in hydroxylamine buffers, acetic acid buffers, and dilute HCl. Rate constants for hydrolysis of the oxime have been measured in the acidity range pH 4-12 M HClO4. At the highest acidities, a reaction pathway via protonated carbinolamine has been identified: evidence is presented that the reverse of this reaction involves rate-determining attack of hydroxylamine upon protonated 9-formylfluorene. By assuming that the attack of hydroxylamine is diffusion-controlled, with rate constant 3 X 10(9) M-1 s(-1), a pK(a) for O-protonation of the aldehyde (-4.5) is derived. Taking account of the equilibrium constant for enolization of 9-formylfluorene (K-E = 16.6), a pK(a) for for C-protonation of the enol tautomer (-5.7) may also be obtained. Comparison of this pK(a) with that of the enol of acetophenone shows that the enol of 9-formylfluorene is less basic by a factor of 10(10). By combining pK(a)s for protonation of the aldehyde and oxime with measured or estimated equilibrium constants for addition of water, hydroxide ion, and hydroxylamine to 9-formylfluorene, it is also possible to obtain values of pK(R) = -5.3, 4.1, and 12.25 for the protonated 9-formylfluorene, protonated oxime, and 9-formylfluorene, respectively. The usefulness of pK(R) in providing a general measure of equilibrium constants for electrophile-nucleophile combination reactions is discussed.

  DOI：

  10.1139/cjc-78-12-1594
• 作为产物：
  描述：

  fluorene-9-carbaldehyde 在 羟胺 作用下， 以 水 为溶剂， 生成 9-甲酰基芴肟
  参考文献：
  名称：

  Rate and equilibrium constants for formation and hydrolysis of 9-formylfluorene oxime: diffusion-controlled trapping of a protonated aldehyde by hydroxylamine

  摘要：

  Equilibrium constants K-add = 440 and K-ox = 3.0 X 10(8) for formation of a carbinolamine adduct and oxime, respectively from 9-formylfluorene and hydroxylamine, and pK(a) = -1.62 for protonation of the oxime, have been evaluated at 25 degreesC in aqueous solution, based on measurements in hydroxylamine buffers, acetic acid buffers, and dilute HCl. Rate constants for hydrolysis of the oxime have been measured in the acidity range pH 4-12 M HClO4. At the highest acidities, a reaction pathway via protonated carbinolamine has been identified: evidence is presented that the reverse of this reaction involves rate-determining attack of hydroxylamine upon protonated 9-formylfluorene. By assuming that the attack of hydroxylamine is diffusion-controlled, with rate constant 3 X 10(9) M-1 s(-1), a pK(a) for O-protonation of the aldehyde (-4.5) is derived. Taking account of the equilibrium constant for enolization of 9-formylfluorene (K-E = 16.6), a pK(a) for for C-protonation of the enol tautomer (-5.7) may also be obtained. Comparison of this pK(a) with that of the enol of acetophenone shows that the enol of 9-formylfluorene is less basic by a factor of 10(10). By combining pK(a)s for protonation of the aldehyde and oxime with measured or estimated equilibrium constants for addition of water, hydroxide ion, and hydroxylamine to 9-formylfluorene, it is also possible to obtain values of pK(R) = -5.3, 4.1, and 12.25 for the protonated 9-formylfluorene, protonated oxime, and 9-formylfluorene, respectively. The usefulness of pK(R) in providing a general measure of equilibrium constants for electrophile-nucleophile combination reactions is discussed.

  DOI：

  10.1139/cjc-78-12-1594

文献信息

• Synthesis and GABA uptake inhibitory properties of 6-aryl iminoxymethyl substituted nipecotic acids
  作者：Victor N'Goka、Tine B. Stenbøl、Povl Krogsgaard-Larsen、Gilbert Schlewer

  DOI：10.1016/j.ejmech.2004.07.003

  日期：2004.10

  Nipecotic acid derivatives bearing an aryl iminoxymethyl side chain at the position 6 were synthesised and tested for their GABA uptake inhibitory properties. Contrarily to the N-substituted derivatives 2, 3 the introduction of the oxime function in the side chain of analogues of the active nipecotic derivative 4 does neither increase, nor maintain the activity. (C) 2004 Elsevier SAS. All rights reserved.